Photographic coupler dispersions

ABSTRACT

Water-insoluble organic solvent-soluble polymers are advantageously mixed with hydrophobic photographic couplers either alone or together with an auxiliary solvent to prepare a coupler composition that is valuable for dispersing in aqueous hydrophilic colloid silver halide emulsion for color photographic elements. The novel dispersions are valuable for preparing photographic elements because they have good sensitometric characteristics, produce layers having improved rigidity even in thin layers and give improved stability to coupler and dyes formed from couplers, as well as provide other improved physical characteristics.

50] Field of Search.

United States Patent 3, 6l9,l95

7 2] Inventor John H. Van Campen 3,451.820 6/1969 Umberger 96/100 Rochester, N.Y. 3,495,986 2/1970 Franco et al 96/100 1 Appl' 772836 Primary Examiner-William D. Martin 22] Filed Nov. 1, 1968 45] Patented Nov. 9, 1971 73] Assignee Eastman Kodak Company Rochester, N .Y.

Assistant Examiner-Bernard D. Pinalto Attorneys-William J. J. Kline, James R. Frederick and Ray Carter Livermore 54] PHOTOGRAPHIC COUPLER DISPERSIONS ABSTRACT: Water-insoluble organic solvent-soluble 19 Claims, No Drawings polymers are advantageously mixed with hydrophobic photo- 5 2] US. Cl 96/100, graphic couplers either alone or together with an auxiliary p 96/7436 14 vent to prepare a coupler composition that is valuable for 51] lnLCl G03c l/40 dispersing in aqueous hydrophilic conoid sHver halide p 7/100, sion for color photographic elements. The novel dispersions are valuable for preparing photographic elements because they have good sensitometric characteristics, produce layers 56] References cued having improved rigidity even in thin layers and give improved UNITED STATES PATENTS stability to coupler and dyes formed from couplers, as well as ,062,653 l l/l962 Weissberger et al 96/100 provide other improved physical characteristics.

1 PHOTOGRAPHIC COUPLER DISPERSIONS This invention relates to color photography including improved color photographic emulsions containing incorporated color-forming couplers and photographic elements containing these improved color photographic emulsions.

Color photographic processes are known in which dye images are prepared by image-wise reaction of an oxidized primary aromatic amino color developing agent with a phenolic or active methylene coupler compound to produce indophenol, indamine, indoaniline, azomethine, etc., dyes.

In some processes couplers, are introduced as a component of color developer solutions used in the color processing. Other color development processes are simplified by incorporating the couplers directly in the light-sensitive film or plate. So-called ballast" groups or radicals are attached chemically to the coupler molecule for the purpose of inhibiting diffusion of the coupler from the layer in which it is incorporated to adjacent layers. It is well known to disperse colorforming couplers in the color-forming layers as a solute or as dispersed droplets or particles comprising a water-immiscible organic liquid in which the coupler is dissolved or otherwise dispersed. A solvent often used for this purpose is tri-cresyl phosphate. The use of such water-immiscible solvents to disperse incorporated couplers in emulsion layers is described, for example, in the Jelley and Vittum US. Pat. No. 2,033,027, issued June i943. While the Jelley and Vittum invention represented a significant advance in the art of incorporating couplers, there remains certain disadvantages. For example, the prior art coupler solvents are oily and tend to soften the film in which they are incorporated. With increased demands for sharper photographic image reproductions, it has been necessary to coat thinner emulsion layers by reducing the amount of gelatin. As the ratio of gelatin to coupler solvent decreases, there is less binder around the particles to make the coated layer rigid. The oily property of the coupler solvent particles makes the thinly coated layerssofter and more subject to abrasion than is desired. Certain prior art coupler solvents interfere with the oxidation of the colorless, reduced leuco-dye formed by the coupling reaction to the color form of the dye, thus making the dye density strongly dependent upon the oxidizing action of the bleach or blix solution and therefore may make it impractical to use blix solutions which often contain relatively weak oxidizing agents.

In order for a compound to be advantageously used as a dispersant for the incorporation of hydrophobic couplers in photographic emulsion layers, it is desired that the compound be immiscible with water, miscible with the coupler preferably having substantial solvent action on the coupler, permeable to processing solutions,that the compound prevent or retard any tendency for crystallization of the incorporated coupler, enhance the coupling reactivity of the coupler with oxidized color developing agent, that the compound has a beneficial affect on the stability of the element containing an incorporated coupler and the stability of the dye formed by the reaction of coupler and oxidized color developing agent, that the compound have no significant affect on the hue of the dye formed, that the compound be resistant to chemical and environmental factors, that the compound not interfere with the bleach in its oxidation of the colorless reduced leuco dye sometimes formed during color development, that the compound have an index of refraction that is as close as possible to the index of refraction of the hydrophilic colloid binder that it is to be dispersed in, etc. Earlier attempts to incorporate couplers in association with polymeric particles have produced dispersions that did not contain the desired amount of coupler or which had unsatisfactory coupler activity.

Dispersing agents for incorporating hydrophobic couplers in the emulsion layers are desired which have the characteristics discussed above and which in addition will increase the strength and abrasion resistance of thin photographic emulsion layers containing couplers, and will not impede the conversion of the colorless, reduced leuco dye often formed during color development to the colored dye by even relatively weak oxidizing agents used in blix solution.

It is therefore an object of my invention to provide novel polymeric dispersing agents that are used advantageously for incorporating hydrophobic couplers in photographic emulsion layers, said dispersing agents having the characteristics desired including promotion of good coupling reactivity, no interference in conversion of any colorless, reduced leuco dyes formed by color development to the colored dyes by oxidation even by weak oxidizing agents that are sometimes used in blix solutions, and no softening or weakening of the thin emulsion layers.

Another object is to provide novel light-sensitive emulsions having couplers incorporated with my novel dispersing agents, said emulsions having layers that are desirably rigid, resistant to abrasion and resistant to damage from pressure.

Another object is to provide my novel photographic lightsensitive elements having my novel emulsion layers containing couplers dispersed with my novel dispersing agents which impart improved physical characteristics including less swelling during processing and higher-melting points, and reduce the tendency for stain formation during incubation as well as dye fading from exposure to light.

Another object is to provide my novel light-sensitive photographic elements having at least one emulsion layer in which a coupler is incorporated with at least one of my novel polymeric dispersing agents, said coupler having good coupling reactivity with oxidized color developing agent.

Still other objects will become apparent from a consideration from the following specification and claims. 7

These and still other objects are accomplished by the preparation of my novel photographic emulsions containing incorporated hydrophobic couplers and the use of these emulsions in light-sensitive photographic elements according to my invention. According to my invention, hydrophobic photographic couplers are mixed with a water-insoluble organic solvent-soluble polymer as a dispersing agent, i.e., vehicle or carrier either alone or together with an auxiliary solvent in which both polymer and coupler are soluble and the resulting mixture is then intimately dispersed in discrete but finely divided particulate form in an aqueous hydrophilic colloid binder.

Although the size of the dispersed polymer-coupler particles can bc'varied over a considerable range, typical particles are of the order of from about 0.5 to about 5 p. in average diameter. The resulting emulsion is then advantageously chill set, noodled, washed with water (preferably distilled water) and/or dried; this procedure will eliminate any solvent used. The hydrophilic colloid containing the substantially uniform dispersion of minute particles of the coupler-polymer mixture is then intimately mixed with the appropriate hydrophilic colloid silver halide emulsion and the resulting emulsion is used in the preparation of light-sensitive photographic elements. The dispersed particles of coupler-polymer mixture in the finished emulsion contain substantially no silver halide. The minute particles of coupler-polymer mixture usually have an average diameter of less than 5 microns and preferably less than one micron and are mutually exclusive of the silver halide grains that are also dispersed in the hydrophilic colloid binder layer. My emulsions are advantageously used in the preparation of color photographic materials that usually contain three differently sensitized emulsions, each containing an appropriate coupler or couplers needed to form the desired images.

My polymeric dispersing agents serve as a water-insoluble organic solvent-soluble, aqueous alkali permeable polymeric vehicle or carrier for my hydrophobic couplers and in some instances, serve as a solvent for my couplers.

l have found that use of the described polymers, especially alkyl acrylate polymers, either alone or together with an auxiliary solvent to disperse hydrophobic couplers in the hydrophilic colloid emulsion produces emulsions that are advantageously used to prepare photographic elements having improved sensitornetric and physical characteristics. For example, my emulsion layers are substantially more rigid and resistant to abrasion than are emulsion layers containing coupler dispersed in the conventional monomeric oily coupler solvents. This improvement is especially noticeable and valuable in thin coatings where the ratio of the amount of hydrophilic colloid binders to the amount of the coupler-polymeric dispersant may be relatively low. My preferred dispersing agents have the valuable advantage of not only providing the improved physical characteristics desired but can be substituted for the conventional dispersing agents without affecting the sensitometric characteristics of the emulsion coatings. I have found that use of my polymeric coupler dispersing agents results in emulsions having improved reactivity and stability of the incorporated couplers and improved stability of the dye images formed from the couplers.

1n the dispersed particles of coupler-polymeric dispersing agent the polymeric component permits permeation by the oxidized color developing agent and other chemicals needed for color development but the polymer seems to act as a barrier protecting the coupling agent and the dye images when formed, from undesirable exposure to deteriorating agents, e.g., oxygen, light, heat and degrading addenda in the photographic element and in photographic processing solutions. Similarly, substantial reduction in stain formation and reduction of unwanted deposits of dye in other layers due to coupler diffusion, obtained with my novel elements, apparently are attributable to the polymeric component in the dispersed particles containing the coupler.

The water-insoluble organic solvent-soluble alkyl acrylate polymers used to advantage as polymeric dispersants for hydrophobic couplers are generally film forming. The preferred polymers are too hydrophilic in character to be prepared in the form of latices, e.g., by emulsion polymerization. Polymers, hydrophobic enough to be made up in latex form, produce coupler dispersions having inadequate coupling reactivity.

Typical polymers used to advantage according to my invention are interpolymers in which the major component represents hydrophobic monomer units such as alkyl acrylates, alkyl methacrylates, etc. My polymers advantageously contain a portion ofa hydrophilic monomer, e.g., acrylic acid, acryloxyalkyl sulfonic acids, N-vinyl-2-pyrrolidone, 2- acetoacetoxyethyl methacrylate, N-cyanoacetyl-N'- methacrylyl hydrazine, etc.

The alkyl acrylate polymeric dispersing agents used advantageously according to my invention include those containing recurring units of the formula:

CH J

=C-OR1 wherein R represents hydrogen or methylrR represents an alkyl group, preferably alkyl having from one to 22 carbon atoms (e.g., methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, octadecyl. docosyl, etc.); alone or together with recurring units of at least one of the formulas:

wherein R is as defined previously; and

wherein R represents hydrogen or alkyl, preferably alkyl having from one to eight carbon atoms (e.g., methyl, ethyl, butyl, hexyl, octyl, etc.

Among the preferred polymeric dispersing agents are those comprising from about 40 to 98 mole percent alkyl acrylate monomer and from about 60 to about 2 mole percent of acrylic acid or acryloxy alkane sulfonic acid.

Included among typical polymeric dispersing agents used according to my invention are the following representative examples.

1. poly( butyl acrylate acrylic acid 15% 2. poly(butyl acrylate 98% acrylic acid 2% sodium salt) 3. poly(butyl acrylate 95% acrylic acid 5% sodium salt) 4 poly(butyl acrylate 3-acryloxybutanel -sulfonic 3- acryloxybutane-l-sulfonic acid 15% sodium salt) 5. poly(butyl acrylate 95% 3-acryloxybutane-l-sulfonic acid 5% sodium salt) 6. poly(butyl acrylate 3-acry1oxybutane-1-sulfonic acid 10% sodium salt) 7. poly(butyl acrylate 85% 3-acryloxypropane-l-sulfonic acid 15% sodium salt) l 8. poly(butyl acrylate 3-acryloxpropane- 1 -sulfonic ]acid 5% sodium salt) 1 9. poly(butyl acrylate 85% acrylamide 15%) i 10. poly(methacrylate 90% acrylic acid 10%) 1 1. poly(methacrylate 95% acrylic acid 5%) l2. poly(stearyl methacrylate 85% acrylic acid 15%) 13. poly(butyl acrylate 95% N-cyanoacetyl-N'-methacryly1- hydrazine 5%) v 1 l4. poly(butyl acrylate 90% N-cyanoacetyl-N'-methacrylylhydrazine 10% 15. poly(butyl acrylate 42.5% stearyl methacrylate 42.5% acrylic acid 15%) 16; poly(butyl acrylate 64% stearyl methacrylate 21% acrylic acid 15%) 17. poly(butyl acrylate 81% 2-methyl-vinyl pyridine 1 2% acrylic acid 3.6%)

18. poly( butyl acrylate 91% 2-methyl-vinyl pyridine 5.4% acrylic acid 3.6%)

19. poly( butyl acrylate 60% stearyl methacrylate 25% acrylic acid 15%) 20. poly(butyl acrylate 68% stearyl methacrylate 17% acrylic acid 15%) 21. poly(butyl acrylate 76.5% stearyl methacrylate 8.5% acrylic acid 15%) 23. poly( butyl acrylate 67.5% stearyl methacrylate 22.5% acrylic acid 10%) 23. poly(butyl acrylate 51% stearyl methacrylate 34% acrylic acid 15%) 24. poly(butyl acrylate 81% acetoacetoxyethyl methacrylate 5% acrylic acid 14%) 25. poly(butyl acrylate 76% acetoacetoxyethyl methacrylate acrylic acid 14%) 26. poly(butyl acrylate 81% N-cyanoacetyl-N-methacrylylhydrazine 10% acrylic acid 9% 27. poly(butyl acrylate 85% N-vinyl-2-pyrrolidone 15%) 28. poly( butyl methacrylate 85% acrylic acid 15%) 29. poly(butyl methacrylate 85% methacrylic acid 15%) Any of the auxiliary solvents used by the prior art for aiding in the solution of hydrophobic couplers can be used to advantage according to my invention. Typical auxiliary solvents included ethyl acetate, chloroform, benzyl alcohol, methyl acetate, propyl acetate, butyl acetate, isopropyl acetate, ethyl propionate, secondary butyl alcohol, etc.

The ratio of polymeric dispersing agent to auxiliary solvent can be varied over a wide range and is dependent upon the particular polymeric dispersing agent and hydrophobic coupler used. At leas enough auxiliary solvent is generally used in order to give the mixture a sufficiently low viscosity so that the mixture can be readily dispersed in the aqueous hydrophilic colloid. Usually the ratio of polymeric dispersing agent to auxiliary solvent is in the range from about 1 to 2 to about 1 to 50. The polymeric dispersing agent usually makes up from about 4 percent to about percent by weight of the mixture of coupler plus polymeric dispersing agent plus auxiliary solvent. The ratio of coupler to polymeric dispersing agent can be varied widely, usually in the range from about 1 to l to about 1 to 100 by weight and preferably in the range from about 1 to 2 to about 1 to 30 by weight.

Any of the hydrophobic couplers used in color photography are used to advantage in my emulsions. These couplers include uncolored color-forming four-equivalent or twoequivalent nondifiusing couplers, colored color-forming nondifl'using couplers, DIR,(i.e., development inhibitor releasing) couplers, etc. ln some instances, mixtures of colorless and colored color-forming couplers and/or DlR couplers are advantageously used. Mixtures of twoand four-equivalent couplers are used advantageously.

As yellow dye-forming couplers, open-chain active methylene couplers are advantageously used including the cyanoacetyl couplers (e.g., the cyanoacetyl coumarone couplers, the cyanoacetylbenzoyl couplers, etc.), the openchain ketomethylene couplers, such as, the acylacetyl couplers (e.g., acylacetanilide couplers, the acylacetamide couplers, etc.). These couplers include those advantageously represented by the formula:

wherein R represents an alkyl group (substituted or not), an

group in which R and X are as described previously], a cyclooxy group [e.g., an aryloxy group (e.g., a phenoxy group, a naphthoxy group, etc.), a heterocycloxy group (e,g., a pyridinyloxy group, a tetrahydropyranyl group, a tetrahydroqinolyloxy group, etc.)], an alkoxy group, an alkthio group and an arylthio group in which these groups are substituted with a wide variety of well-known groups and also a group in which R and X are as defined previously, a monothio group [e.g., a phenylthio group, a heterocyclicthio group (e.g., a tetrazolylthio group, a triazinylthio group, a triazolylthio group, (etc.), an alkylthio group, etc.], a 2- aminoarylazoxy group, a 2-amidoarylazoxy group, a Z-aryltriazolyl group, a phenylazo group; etc.. in which at least one of the groups R, Xor Ycontains substituents which ballast the coupler to make it hydrophobic and nondiffusing in hydrophilic colloid layers.

Typical couplers include the following:

1. w(p-benzoylbenzoyl) acetanilide 2 w-benzoyl-p-sec.-amylacetanilide 3. N,N-di (m-benzoylacetyl)-p-phenylenediamine 4. a- {3-[a-( 2,4-di-tert-amylphenoxy)butyramidol-benzoyll 2-methoxyacetanilide 4,4'-di-(acetoacetamino)-3,3'-dimethyldiphenyl p,p'-di-(acetoacetamino)diphenylmethane N-phenyl-N'-(p-acetoacetaminophenyl)urea N(w-benzoylacetyl) 1,2,3 ,S-tetrahydroquinoline N(w-benzoylacetyl)morpholine O. a-O-methoxybenzoyl-a-chloro-4-Ia-(2,4-di-tertamylphenoxy)-n-butyramidolacetanilide 1 1. a- {3-[a-(2,4-di-tert-amylphenoxy)butyramidoIbenzoyl} -a-fluoro-2-methoxyacetanilide 12. a-fluoro-a-piva1y1-5-[y-(2,4-di-tert-amylphenoxy) butyramidol-2-chloroacetanilide I 13. a-acetoxy-a-{ 3-[y-( 2,4-di-tert-amylphenoxy)-butyramido lbenzoyl l -2-methoxyacetanilide 14 a-[4-( 4-hydroxyphenylsulfonyl)phenoxyl-a-pivalyl- 2- ch1oro-5-[y-( 2,4-di-tert-amylphenoxy)butyramido]a cetanilide 15. a-{ 3-['y-( 2,4-di-t-amylphenoxy)acetamido lbenzoyl} -a- 1-phenyl-5-tetrazolylthio)- 2-fluoroacetanilide phenylazo-2-fiuoroacetanilide The hydrophobic couplers of US. Pat. Nos. 2,875,057, 2,908,573, 3,046,129, 3,227,155, 3,265,506, 3,384,657, 2,778,658, 3,253,924, 3,227,550, 3,227,554, French Pat. No. 90319, French Pat. No. 1,291,110 and Canadian Pat. No. 792,238 are incorporated herein by reference.

Any of the well-known hydrophobic magenta dye-forming couplers used in photography are used to advantage according to my invention. These couplers include S-pyrazolone couplers having the formula:

wherein R is as described previously; R represents a group such as an alkyl group, substituted carbamyl, an amino group (substituted or not with one or two alkyl groups and/or one or two aryl groups), a substituted amido group e.g., a benzamido group (substituted or not), an alkamido group (substituted or not); Y represents hydrogen (in four-equivalent couplers), or

a, coupling off group (in two-equivalent couplers), e.g., thiocyano, an acyloxy group, an aryloxy group, an alkoxy group, chlorine, fluorine, sulfo, a phenylazo group, a monothio group [e.g., a phenylthio group, a heterocyclicthio group (e.g., a tetrazolythio group, a triazinylthio group, a triazolythio group, etc. an alkylthio group, etc. a 2-aminoarylazoxy group, a 2- amidoarylazoxy' group, a 2-aryltriazolyl group, etc., in which at least one of the groups R, R and Y includes a ballast group that makes the coupler hydrophobic. Typical couplers include the following:

1. Z-cyanoacetylcoumarone-5-( N-y-phenylpropyl )-p-tertamylsufonanilide 2. l-p-laurylphenyl-3methyl-5-pyrazolone 3 l .4-phenylene bis-3-( l-phenyl-S-pyrazolone) 4 l-phenyl-3-n-valerylanino-5-pyrazolone 5 l-phenyl-3-(p-sec.-amylbenzoylamino)-5-pyrazolone 6. l-(p-phenoxyphenyl)-3-(p-tert-amyloxbenzoyl)amino-S- pyrazolone 7. l-( 2',4,6'-trichlorophenyl)-3-benzamido-5-pyrazolone 8. l-( 2',4',6'-tribromophenyl )-3-phenylacetamido-5- pyrazolone 9. l-( 2',4-dichlorophenyl)-3-[3"-(2", 4", di-tertamylphenoxyacetamido)benzamido1-5-pyrazolone l0. l-(2,4',6'-trichlorophenyl)-3-[BB-(2"', 4"'-di-tertamylphenoxy)propionamido]-5-pyrazolone l l. l-(2',5'-dichloro)-3-[3"-(4"'-tert-amylphenoxy)- benzamido]-5-pyrazolone 12. l-( 2,5'-dichlorophenyl)-3-[ 3 2 4' -di-tertamylphenoxyacetamido)benzamidol-5-pyrazolone l3. l-(2,4,6-trichlorophenyl)-3-(4-nitroanilino )-4- steroyloxy-S-pyrozolene 14. l-( 2,4,6-trichlorophenyl)-3-{ 3-[ a-( 2,4-di-tertamylphenoxy)acetamidoIbenzamidol -4-acetoxy-5- pyrazolone l5. l-( 2,4,6-trichlorophenyl)-3-pentadecyl-4-thiocyano-5- pyrazolone 16. l-( 2,4,6-trichlorophenyl)-3-pentadecyl-4-sulfo-5- pyrazolone l7. l-[4-3,S-dicarboxybenzamido)phenyl]-3-ethoxy-4-( 3- octadecycarbamylphenylthio)-5-pyrazolone l 8. l-phenyl-3-octadecylamino-4-( l-phenyl-S-tetrazolylthio )-5-pyrazolone I9. I-( 2,4,6-trichlorophenyl )-3-[3 2",4' "-di-tamylphenoxyacetamido)benzamidoih-4-phenylazo-5- pyrazolone l- 4-[a-(3-t-butyl-4-hydroxyphenoxy )tetradecanamido ]h2,6-dichlorophenyl -3-( 2,4- dichloroanilino )-5-pyrazolone 21. l-( 2-chloro-4,6-dimethylpheriyl)-3-[ a-( 3-t-butyl-4- hydroxyphenoxy)tetradecanamidol-5-pyrazolone 22. l-( 2-bromo-4,6-dichlorophenyl )-3-{ 2-chloro-4-[B- (2,2-dimethyl-6-hydroxy-7-octadecyl-4-chromanyl propionamido]anilino}-5-pyrazolone The hydrophobic couplers of U.S. Pat. Nos. 2,600,788, 2,80l,l7l, 2,908,573, 2,983,608, 3,046,] 29, 3,062,653, 3,227,554 and French Pat. No, l,529,896 are incorporated herein by reference.

Any of the well-known hydrophobic phenolic and naphtholic cyan-forming couplers are used to advantage in my invention. These couplers include those having the formulas:

OH OH 811d 3. m R

l R y: a

wherein R represents hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group (e.g., amino, alkylamino, arylamino, heterocyclic amino, etc.), a substituted carbonamido group (e.g., an alkylcarbonamido group, an arylcarbonamido group and a heterocyclic carbonamido group), a substituted sulfonamido group (e.g., an alkylsulfonamido group, an arylsulfonamido group, a heterocyclic sulfonamido group, etc.), a substituted sulfamyl group (e.g., an alkylsulfamyl group, an arylsulfamyl group, a heterocyclic sulfamyl group, etc.), a substituted carbamyl group (e.g., an alkylcarbamyl group, an arylcarbamyl group, a heterocyclic carbamyl group, etc), a hologen atom (e.g., chlorine, bromine, etc.); R", R and R each represent any of the groups represented by R and in addition an alkoxy group, and R, R", R and R are advantageously further substituted by any of the ballasting groups well known in the art; Y represents any of the groups previously defined for Y but does not represent an aryloxy group; and Y" representsthe groups previously defined for Y and also includes a cyclic imido group (e.g., a maleimido group, a succinimido group, a l,2-dicarboximido group, a

phthalimido group, etc.), such that at least one of the groups 5 R R", R, R Y and Y ofa coupler contains sufficient ballast to make the coupler hydrophobic and non-diffusing.

Typical hydrophobic cyan dye-forming couplers include:

I. 5-( n-benzyl-N-n-valerylamino)- l -naphthol 2. S-caproylaminol -maphthol l 2-chloro-5-( N-n-valeryl-N-p-isopropylbenzylamino)- l naphthol 4. S-diphenylethersulfonamidol -naphthol 5. l-hydroxy-2 -(N isoamyl-N-phenyl )naphthamide 6. phenoxyacetaminol -naphthol 7. 2-a-(p-tert-amylphenoxy)-n-butyrylamino-5-methylphenol 8. l-hydroxy-N-[ o-( 2,4-di-tert-amylphenoxy )butyl 2- naphthamide 9. 2-(4-tert-amyl-3-phenoxybenzoylamino)-3,5- dimethylphenol l0. l-hydroxy-4-acetoxy-N-[a-(2,4-di-tert-amylphenoxy)- butyII-Z-naphthamide l l. l-hydroxy-4-thiocyano-N-[ a-2,4-di-tert-amylphenoxy butyll-2-naphthamide 12. l-hydr0xy-4'(pentafluorophenoxy)-N- {B {4-[a-( 2,4-di

tert-amylphenoxy )acetamidolphenyll ethyl}-2-naphthamide-naphthamide l3. l-hydroxy-4-( 4-chlorophenoxy )-2'-tetradecyloxy-2- naphthanilide I4. l-hydroxy-4-phenyl-4'-(p-tbutylphenoxy)-2- naphthanilide l5. l-hydroxy-4-( l-phenyl-5tetrazolylthio )-2-tetradecyloxy-Z-naphthanilide l6. 2-(3,5-dichlorosulfonylbenzamido )-5-methyl-4-( l-phenyl-S- tetrazolylthio )phenol The hydrophobic cyan dye-forming couplers of US. Pat, Nos. 2,423,730, 2,474,293, 2,52l,908, 2,80l,l7l and 3,227,554 are incorporated herein by reference In addition to the image-forming couplers, other hydrophobic addenda such as competing couplers, stabilizers, ultraviolet absorbers, antistaining agents and polymeric plasticizers are incorporated, if desired, in my polymeric dispersing agents.

Any of the film-forming hydrophilic colloid binders used in photography are advantageously used in making my emulsions, including colloidal albumin, cellulose derivatives, synthetic resins (e.g., a polyvinyl compound), gelatin, and mixtures of gelatin with a synthetic resin.

in a preferred process for making my photographic couplerpolymer dispersions, a ballasted coupler and a relatively hydrophilic, water-insoluble film-forming polymer are dissolved in a common water-immiscible volatile organic solvent and the resulting solution is emulsified in an aqueous solution or sol of a hydrophilic film-forming binder such as gelatin, to form an emulsion having fine droplets of the volatile solvent containing dissolved polymer and coupler dispersed in the aqueous phase. This composition is set, for example, by chilling, then the set composition is noodled and'substantially all of the solvent removed by evaporation at room temperature or by washing. This procedure results in a substantially uniform dispersion of discrete particles of the couplerpolymer mixture in the hydrophilic colloid binder. This dispersion is intimately mixed with an appropriate light-sensitive emulsion of one or more silver halides dispersed in aqueous hydrophilic colloid binder such as gelatin. Any of the lightsensitive silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc., are used to advantage in my emulsions. My invention is primarily directed to the ordinary silver halide developing out emulsions. Particularly useful results are obtained with gelatino-silver-chlorobromide emulsions. Usually the cyan dye-forming coupler-polymer dispersion is added to an emulsion that is spectrally sensitized to red light, the magenta dye-forming coupler-polymer dispersion is added to an emulsion that is spectrally sensitized to green light, and the yellow dye-forming coupler-polymer dispersion is added to an emulsion that is sensitive to blue light or that has been spe ra y sen ti d to blue ligh pe i i z t n a ehemieal sens a i n wh n s ed a ac mp i h d by oneh e al n we -kn w m an Th usual spe t sens i t e ye a e u ed. u h a he yan nes. m ru ya i es. eemp e rinuciear) eya in s, compl x rinu' l a m roeyanihes. e y y et ieyan hes. t T se dy ca ee ta h th u ua b s nu ei e-g-- ia e e, eh h azoie, haphtho hieze e ben az aphth xazele. h hze e ha hl naph he e e a el t qu ne n y u in h as o the me eey nin dyes sueh hue e a r an ne, 2= th hy a oiu, exazeledi ne. pyra ehe, ete- Su h dye for examnle a e descri ed in Brooker usher N 12.185. 2- 2 24l 37 arr ll U- Patos 2 6 ,9 1, 2. 2 H seh in t al- U-S- Pat- Nos 2 666.7, C l al- U-S- Pa No, 2 0 715. e The ilver hali e mul i n eah also c ntain ny of the other a i nda use in pho og aphi emul ienev s, hemi a seh i z r a t eizizau sY ha d ne stab z agents, coating aids, etc. i

T e mul ons Prepared i ae or anee w t my nvent on re a vantageou ly oated in th onve i n manne up n any u a uppor s. gla s. ose n ate m, ee lu= s a ta e film, Polyviny aeeta resi lm. po ycar o at m. P ysty ene lm; polyester film. me al, p per an ther fi ou upp t m eri..,.

U lly my emulsion are e ated n m l i ayer e lo phot a c e m n ha g at east thre di er y sen tized mulsion layers ee t d ever ne ano her o a SUPPQH' Usual y e upp rt s co t d. s eees i elyt with a red-sensit aye a een-s i iv l yera d a blu e si ve aye and usual y but not necessarily with an ultraviolet and blu filter layer betw en th iue en itive an green-sen it e ayers. r he p r s c ted eeessive y w t th b ue-se i i e l y the greeni ensitive layer and the red-sensitive layer. The three sensitized layers may be arranged in any other order over one er hat is s a l howe er. h ue fi te o ou ly w u d n t be put. o e he ue-s i ive ayere erably? th se light-se sit ve lay rs a e ra ged n he ame id of the support.

Fu her dvan age in image e a y a e ned sinc my' polymers, unlike many prior art vehicles have a refractive index close to gelatin. However, it was completely unexpected at th P ymers m yed in y pr e s, uld imp ove he stability to ultraviolet radiation of the coupling agents and the dy ter ther f om i he. proe es f e e de opm since these polymers are highly transparent to such radiation. hy e e w'el kuew Prima y a m ie amino ee o ermi s lve alide develop ng agen s such a t e ph ny e iamin e. -2-- die hy -P-pheny hediamine yd o h o ,Y m. he n thy p-Ph yleuediam e y ro h ri e. dime hyl-p-phe yle e iautih i ll t yl- -(fi yd ye hy .)amih iahilih e e-t e pthi opheh ls a he u tu ion pr du t whe e the amin gr up is n ubr stituted can he used c or de e op pho og ap i oa ng ai n he QQHPIQF'POIYWCY Pat ie e f m in n ion: Various he mate al n b ncluded n he developer utions depending upon h pa tieular eq irem nts. f r am- PIC, n kal metal ulfi e. e rbona e isul r mide. de an i he h k ni g agent sed n ise us d v leper e thrt s t such a r hyt xye hyl ell ose an b xymethyt'eeliulese he o ow ng e amp es are iu u ed e a ur h r undet t hd ns f hy nventi n EXAMPLE I amylphenoxy)butyrarnidolacetanilide. a yellow dye-forming ballasted coupler of the type described in Weissberger et al. U .S. Pat. No. 3,384,657, issued May 21. 1968, and two parts of poly(bntyl aerylate acrylic acid) are dissolved with good stirring in 8.1 parts of ethyl acetate at 60 C. The resulting solution is added to a stirred mixture at 55 C. of 12.6 parts of to percent gelatin and 0.3 parts ofa 10 percent aqueous solution of wettinggent tri-isopropyl naphthalenesulfonate. The resulting dispersion is milled five times in a colloid mill to produce particles of the coupler-polymer mixture having an average diameter of less than 5 microns. chili set, noodled and dried. The dried material is reconstituted for use by soaking in water and then stirring mechanically at 40 C.

similarly, my novel process is used to advantage for the incorporation in my polymeric dispersing agents of other commottly t d ballasted color coupling agents.

EXAMPLE 2 Two multilayer color photographic elements containing the same color coupling agents are prepared:

1. my multiiayer element in which the couplers are incor poi-ated by. the method of my invention as illustrated in e a ple I an 2. a control.

My multilayer element is prepared as follows: on a paper support are coated in succession, layer l consisting of a bluesensitive, silver ehlorobromide gelatin emulsion containing the yellow image-forming coupler of example I; layer 2, a gelatin interlayer; layer 3, a green-sensitive silver ehlorobrornide gelatin emulsion containing l-( 2-chloro-4,6- dimethy bhe yD -l -t -P n y P y lbu y l bengamido-5-pyra zolone, a magenta image-forrning coupler, described in US. Pat. No. 3,062,653, issued Nov. 6, 1962;

layer 4, a red-sensitive, silver ehlorobromide gelatin emulsion containing 2-[a-(2,4-di-tert-amylphenoxy)-butyramido]-4,6- dichloro-S-methyl phenol, a cyan image-forming phenolic coupler, described in US. Pat. No. 2,801,171, issued Dec. 20, 1954; and layer 5, a protective gelatin overcoat. Each coupler is dispersed in its respective emulsion layer as minute particles of coupler-polymer mixture by the procedure of example I using poly(butyl methacrylate acrylic acid) as the polymeric dispersing agent or vehicle and ethyl acetate as the auxiliary solvent. The gelatin. silver. coupler and polymer spreads for e ch ayer are ollows Silver in the control, the color coupling agents are dissolved in conventional waterinsoluble, organic crystalloidal solvents as in example 2 ofU.S. Pat No. 2,956,879. issued Oct. 18, 1960,

prior to dispersion in the respective layers of the photographic elem nt- The two multilayer coatings are exposed for one half second through a No. 1) color tablet and a +0.66 neutral density filter on an Eastman lB Sensitometer to a 500 watt incandescent lamp and given identical processing through the process described in example I of VanCarnpen US. Pat. No. 2,956,879, which process is incorporated herein be reference: The process uses the steps: color development, stop, fix, wash, bleach, wash, hardener-fix, wash, hardener, wash, buffer and dry.

One part by weight of qapivalyl z-chloro-5-['y-(2,4-di-tert- The following results are obtained:

TABLE I D max. l) min. Log E sptml tlilitltilt't M (outing lit?! tirit'n Bluo Rml tin-er; V B1110 fl ltml tin-on llluo 1.4..." Z 10 1. 98 1.92 000 0:13 0.17 l. 1ll l0. 10 2 (Control) 2 26 2. 00 2. 04 (l. 09 0. l3 0. l6 (outrol These results show that the sensitometric properties of the multilayer color photographic element are substantially unaffected by the polymeric dispersing agent of my invention EXAMPLE 3 The processed elements of example 2 above are given extended exposure to heat and light in conventional testing equipment. The results show that the dyes in the sample prepared by my process exhibit greater stability to heat and light than the dyes in the sample containing conventional coupler solvents.

EXAMPLE 4 In a repetition of example 2, poly(butyl acrylate acrylic acid) is replaced by poly(butyl acrylate 3-acryloxybutanesulfonic acid). Here also it is found that the sensitometric properties and coupler reactivity of the processed multila'yer color elements are relatively unaffected by the polymer. Further, exposure of the image dyes in the above processed element under the conditions described in example 3 give results similar to those obtained in that example.

Similar results are obtained when example 4 is repeated with other polymeric dispersing vehicles, such as poly(butyl methacrylate 3-acryloxybutanesulfonic acid), and poly(butyl methacrylate 3-acryloxypropanesulfonic acid).

Another advantage of my polymeric-coupler particles is their adaptability to difierent types of color processing. For example, it is known that in processing photographic elements containing color couplers dispersed in conventional coupler solvents, such as tri-o-cresyl phosphate or di-nbutyl phthalate, that a strong-acting bleaching agent, such as potassium ferricyanide, is needed in order to obtain a good yield of dye from the colorless leuco dye that is formed in the reaction of coupler with oxidized color developing agents. Mild oxidizing agents, such as the complex of ferric chloride and ethylenediaminetetraacetic acid tetrasodium salt, give low dye yields. However, when the couplers are incorporated by my process, the yield of dye is good and is substantially independent of the nature of the oxidizing agent.

EXAMPLE 5 Four single layer gelatin-silver chlorobromide coatings are prepared that are similar in composition to layer l of example 2 above. In two coatings, the couplers are incorporated by my process using poly(butyl acrylate acrylic acid). The remaining two coatings serve as controls in which the couplers are incorporated as in the control sample of example 2. Samples of the two coatings are exposed as in example 2 and processed in the same manner as that described for example 2 except that a single blix bath (formula below) is substituted for the separate separate fix hath and bleach hathi Control ul'Examplc 2 but 45 24 llh single blix replacing for and bleach Control of Example 2 (with (ontml separate fix bath and bleach bath) The samples are coated at 55 mg. silver sq. ft. The density obtained in the samples given the process of example 2 with separate blix and separate bleach bath is taken at l00%.

EXAMPLE 6 Separate pieces of paper support are coated with gelatino silver halide emulsions containing a dispersion of the yellow coupler used in example I with the prior art monomeric dibutyl phthalate or with my polymeric dispersing agent poly(butyl acrylate acrylic acid) or poly(butyl acrylate 3- acryloxybutane-l-sulfonic acid sodium salt) in the ratios indicated in the table below and each coating is given a protective overcoat of I00 mg. gelatin/ft. The coatings are exposed for one half second through a 0.15 log E step wedge and a 2.0 neutral density filter on an Eastman lB Sensitometer to a 500 w. incandescent lamp and processed through the process used in example 2. The following table summarizes the results:

% 3-m-ryloxyhutnnv-l-sullonitm-ld 15% sodium salt).

The results show that my polymeric dispersing agents do not substantially alter the sensitometric results from those ob,- tained with prior art monomeric di-butyl phthalate. My coatings, however, show the technical advances over the control coatings mentioned before, in that the residual coupler and the dyes formed by color development have improved stability to exposure to ultraviolet light, the images are sharper, and my coatings give good yields of yellow dye even when a blix solution (with a mild oxidizing agent) is used in place of a separate fix and a separate bleach. in addition my coatings have a more rigid structure and are less subject to abrasion. The photographic relative speeds of my coatings 2 and 4 are comparable to the respective control coatings l and 3.

EXAMPLE 7 A paper support coated with a green-sensitized gelatino silver halide emulsion containing a dispersion of a mixture of one part of magenta coupler l-( 2-chloro-4.6-dimethylphen-' yl)-3-[a-(3 -pentadecylphenoxy)butyramidolbenzamido-S- pyrazolone and one part of poly(butyl acrylate 85 percent acrylic acid l5 percent when exposed as described in example 6 and processed as in example 2 gives a photographic relative speed that is comparable to the relative speed given by a control coating having the same silver halide emulsion and coupler but tri-cresyl phosphate in place of my polymer (and using two parts of coupleito Bile part of coufir solvent). A paper support coated with a red-sensitized gelatino silver halide emulsion containing a dispersion of a mixture of one part of cyan coupler 2-[a-(2,4-di-t-amylphenoxy)butyramido]-4.6 -dichloro-5-methyl phenol and one part of poly(butyl acrylate 85 percent acrylic acid percent) when exposed as described in example 6 and processes as in example 2 gives a photographic relative speed that is comparable to a control coating of the same silver halide emulsion and coupler but dibutyl phthalate in place of my polymer (and using two parts of coupler to one part of coupler solvent). Similar results are obtained when these comparisons are made between the same controls and my coating in which poly(butyl acrylate 85 percent 3-acryl-oxybutane-l-sulfonic 15 percent sodium salt is substituted for the polymer used previously. When the processed coatings made in this example are given prolonged exposure to light, my coatings exhibit less print out than do the respective control coatings.

EXAMPLE 8 Coupler: dispersing Dye loss agent (in at max.

parts by density of Coating Dispersing agent weight) 1.0, percent 1 (control) Dibutyl phthalate 1;% 3

2 Poly (butyl acrylate 85% 1:14 27.4

acrylic acid 15%).

Similar reductions in dye loss are obtained when this example is repeated using other polymers of my invention to disperse the yellow coupler. Especially efficacious are my polymeric dispersing agents numbered 1 through X 8, l3, I4, 17 and i8.

EXAMPLE 9 Pieces of paper support are coated with the yellow imageforming, or the magenta image-forming layers indicated below. The coatings are exposed and processed as described in example 2 to give the results summarized below:

Coupler; dispersing agent. (in parts by Relative Layer Disporsing agent weight) speed Yellow (control). Dibutyl phthalate 1:% 100 Yellow- Poly hut-yl acrylate 1:2 8..

9?)- iilagcnta (co11trol) 'Ii'i-t-rcsylpl1ospliate 1:1 100 Magenta i'olybutyl acrylatcv 1:1 83

The use of my polymeric dispersing agents appear to be especially advantageous when part of the gelatin binder is replaced by a nongelatin hydrophilic colloid binder. The following example will illustrate this.

EXAMPLE 10 Pieces of a paper support are coated with cyan layers using the coupler of example 2 and the indicated dispersing agent.

These coatings are exposed and processed as described in example 2 giving the following data.

45 mg. butylacrylate (9091 )-acrylic acid 10' )/ft.'

These data show that replacement of part of the gelatin with a nongelatin hydrophilic colloid binder such as poly(butyl acrylate 90 percent acrylic acid 10 percent) raises the relative speed of my cyan layer from 71 to 89.

The optimum ratio of coupler to polymer and optimum ratio of gelatin to nongelatin hydrophilic colloid will depend upon the particular coupler to be used and can be readily determined by methods well known'in the art.

EXAMPLE 1 1 Pieces of a paper support are coated with a gelatino silver halide emulsion containing the yellow dye-forming coupler used in example 2 mixed with the dispersing agent indicated below. The coatings are exposed and processed as described in example 2.

Coupler Dispcrsing Agent (in Parts by Cualing Dispersing Agent Weight) D max I Di-hutyl phthalate 1:: 2.14

(control) 2 Polytbuiyl acrylate II? 2.25

EXAMPLE l2 Example 11 is repeated but using a redsensitized gelatino silver halide emulsion containing the cyan dye-forming coupler used in example 2 mixed with the dispersing agent indicated below.

Coupler.

Dispensing Agent (in Parts by Coating Dispersing Agent Weight) D max I Di-huty| phthalate l:-.| 2."!

(control) 2 Poly-(hutyl acrylatc lz2 2 42 i acrylic acid IS'Z) EXAMPLE 13 Example 1 l is repeated but using a green-sensitized gelatino silver halide emulsion containing the magenta dyeforming coupler used in example 2 mixed with the dispersing agent inasemscwxyflhyl melhasryluic dicated below acrylic acid 14%) a Poly(butyl acrylate 76% w. 2. 26

acetoacetoxyethyl meth- Coupler: acrylate acrylic acid Dispersing 5 14%) Agent (in Parts by Coating Dispersing Agent Weight) D miix 17 l Tri-crcsyl phosphate l:l |.9 A green-sensitized gelatino silver halide emulsion is made 2 yw y acrylate 95% III 108 ,0 and the magenta coupler described in example 2 is dispersed in one portion of the emulsion with tri-cresyl phosphate as acid 5% sodium salt) 3 do 1% 108 control and in another portion of the emulsion with the 4 Polylbutyl acryliile 95'; 1:1 218 polymer of my invention indicated below. A single layer coaty y v 5 ing is made on a paper support for each emulsion. One set of 5 5% j? 1% 2 M l these freshly made coatings is exposed and processed as 6 poly(mflhylacrylm 2, described in example 2. Another set is incubated for 7 days at acrylic acid i0 1 70 F./50% RH then given the same exposure and processing that the set of fresh coatings were given. D min. data from EXAMPLE 14 these coatings are summarized below. Example 1 l is repeated but using a red-sensitized gelatino silver halide emulsion containing the cyan dye-forming cou tfuu ii-r: l) min. pler used in example 2 mixed with the dispersing agent inf l l'f f'g 'h dicated below. parts by (lays in- Coating Dispensing iigi-nt \vi'iglii Fn'sli t-iilnitiun Coupler: 25 Disper ng 1 (control) i. Tri-t-iesyl-pliospliziiv. 1:1 .10 .30 Agent (in 2. .v Poly (hiityl iii-ryliito 1:, .10 .20

P t b C y N -iiivtliiit'i'ylyl outing Dispersing Agent Weight) D max hymnwilw 109.)

l Di-butyl phthalnte III/Z 1.01 M h b I D f 2 Pmywmymwmc H 4 y coating s ows su stantia y es increase in min. rom stearyl rnethiicrylatc 2m accelerated preexposure keeping than the control coating. ln acryiis acid a comparison of another control coating with a coating conh taining the magenta coupler dispersed with poly(butyl acry- Slmllar results are Obamed when the P y above 5 late 42.5% stearyl methacrylate 42.5% acrylic acid ISZ) my replaced with: coating gives no increase in D min. caused by incubation while p y( u y acrylate 60% stearyl methacrylate acrylic acid the control in this comparison does show an increase in D min. 15%) poly(butyl acrylate 68% stearyl methacrylate 17% acrylic acid EXAMPLE 8 I592) 40 P y y acrylate 765% stearyl methacl'ylate 35% ylic Example I? is repeated but using another green-sensitized acid 15%) gelatino silver halide emulsion and the dispersing agents inpoly(butyl acrylate 67.5% stearyl methacrylate 22.5% acrylic di b l acid 10%) poly(butyl acrylate 51% stearyl methacrylate 34% acrylic acid (ouplor' l) min 15% dispersing agent (in lAlli-r 7 pints iy il iii- EXAMPLE l5 Coating Dispi-rsiiig inn-iii. weight) l-rvsli i'iiliiiiiiiii Example 1 l is repeated using a different gelatino silver hay 1 (control) 'iri-i-n-s iiims hiiii-. l:l ll) .24 lide emulsion and the coupler dispersing agent included "a?!"Q fl flflfi m ,1 A below: pyiroliiliilii- 15%) "P Example 19 Dispersing fi Example 17 is repeated but using a blue-sensitive urs y s i s gelatino silver htllldtl (llllllMOll and tho dispersing agents. Coating Dispersing 2 Weight) D max I indicated e o i Di-butyl phthalale i= 2.04 j [WWW 2 poly(twyl acryla'e 12104 I dispersing in l) iniii. cet lvin l ether 21% agent (in lllllSLii by acrylic acid [5%) llilllS by 7 (hiya of Coating Dispensing lllltllt \\'(ll 'lll) iiii-iiliiitihii 1 i l)ihutyl plitlizilniil: l .05 EXAMPLE l6 2 i'oi niui i iii-r iiiiitit"; i-i i i l:l L02 vinyl (lllll' '31"; 1\l'l' \'lit'ltl'iil 65 1 Example ll is repeated but using a red-sensitized gelatino silver halide emulsion containing the cyan dye-forming coupler used in ex mple 2 mixed h th i p r ng g n in- The data in examples l8 and 19 Show that the D min of my dic l l coatings is increased substantially less than the control by accelerated precxposure keeping.

Coupler: Dispcrring "emu" EXAMPLE 20 Parts by Coating Dispersing Agent Weight) 0 mi Coatings are made on paper support of appropriately sensitized gelatino silver halide containing the indicated coupler I Tri-cm i phosphate l:l 2.20 of example 2 and the indicated dispersing agent. The dye den- Polythuiylacrylatefll'i i;v. 232 sities developed in the exposed and processed coatings are measured and then measured again after 4 days exposure to a Xenon Arc.

Coating Coupler Dlspersing agent Dye fading 1 Cyan. Dibutyl phthalate Control.

2 ..do Poly(bt1tyl acrylate 85% Less than control.

iq-vinyl-2-pyrrolidone 3 Yellowm. Dibutyl phthalate Control.

4 ..do Poly(butyl acrylate 85% Less than control.

N-viuyl-Z-pyrrolidone 15 a 5 Magenta. Tri-cresyl phosphate Control.

6 .-do Poly(butyl acrylate 85% Less than control.

N -viny1-2-pyrrolidono 15% 7 do Poly methyl acrylate Do.

96% acrylic acid 6%).

8 d Poly(stearylmcthacry- D0.

late 85% acrylic acid 15%).

EXAMPLE 21 Example I7 is repeated to compare the control against coatings using my polymeric dispersing agents listed below.

2-rnethyl-5-vinyl pyridine stearyl methacrylate 25% stcaryl methacrylatc 22.5%

stcaryl mcthacrylate 17% stcaryl rncthacrylate 8.5%

In each case the incubation produces substantially less increase in D min. in coatings containing my polymeric dispersing agents than in control coatings.

EXAMPLE 22 Example 17 is repeated but using red-sensitized gelatino silver halide, cyan coupler (of example 2) and dibutyl phthalate (for control) and my polymers:

Poly(butyl acrylate 68% stearyl methacrylate 17% acrylic acid 15%) Poly( butyl acrylate 76.5% stearyl methacrylate 8.5% acrylic acid 15%) Poly( butyl acrylate 98% acrylic acid 2% sodium salt) The D min. values are raised less in my coatings than in the control by incubation. Similar results are obtained when this is repeated using blue-sensitive gelatino silver halide and the yellow coupler of example 2 to compare my polymers against the dibutyl phthalate control.

EXAMPLE 23 A multilayer color photographic element is made as described below. A yellow coupler dispersion is made by dissolving 2 parts by weight of poly(butyl acrylate 85 percent acrylic acid l percent) in 4 parts by weight of ethyl acetate by stirring mechanically, adding to the solution with mixing 1 part by weight of the yellow coupler used in example 1, adding the resulting solution to a mechanically stirred l0 percent aqueous gelatin solution containing a wetting agent. The resulting dispersion is passed five times through a colloid mill to reduce the size of the particles of coupler-polymer ethyl acetate solution so that after evaporation of ethyl acetate the particles have an average diameter less than about 5 microns. After chill-setting, the dispersion is noodled and dried at room temperature. The dried material is reconstituted by soaking in water and stirring, and the resulting dispersion is added to a blue-sensitive silver chlorobromide gelatin emulsion. A magenta coupler dispersion is made by dissolving 1 part by weight of poly(butyl acrylate 85 percent acrylic acid per- LII LII

cent) in 4 parts by weight ofethyl acetate by stirring, adding to the solution with mixing, a mixture comprising 4 parts by weight of the magenta coupler used in example 2, and 6 parts by weight of ethyl acetate and adding the resulting solution to a mechanically stirred 10 percent aqueous gelatin solution containing a wetting agent. The resulting dispersion containing magenta coupler is passed five times through a colloid mill to reduce the size of the particles of coupler-polymer ethyl acetate solution so that after evaporation of the ethyl acetate, the particles of coupler-polymer mixture have an average diameter less than about 5 microns. After chill-setting, the dispersion is noodled and dried at room temperature. The dried dispersion containing magenta couplei is reconstituted by soaking in water and the resulting dispersion is added to a green-sensitized silver chlorobromide gelatin emulsion. A cyan coupler dispersion is made by dissolving l part by weight of poly(butyl acrylate percent acrylic acid l5 percent) in 4 parts by weight of ethyl acetate, then dissolving 4 parts by weight of the cyan coupler described in example 2 in the solution, and dispersing the resulting solution in a l0 percent aqueous gelatin solution containing a wetting agent by mixing and passing through a colloid mill five times to reduce the size of the particles of coupler-polymer ethyl acetate solution so that after evaporation of ethyl acetate the particles of couplerpolymer have an average diameter less than about 5 microns. After chill-setting the dispersion is noodled and dried at room temperature. The dried material containing the cyan coupler is reconstituted as described previously and the resulting dispersion is added to a red-sensitized silver chlorobromide gelatin emulsion. A paper support is coated in succession with a layer of the blue-sensitive silver halide emulsion containing my yellow coupler dispersion, a gelatin interlayer, a layer of the green-sensitized silver halide emulsion containing my magenta coupler dispersion, an ultraviolet absorbing layer, a layer of the red-sensitized silver halide emulsion containing my cyan coupler dispersion, and a gelatin overcoat layer. Good color reproductions are made by image exposure and processing my multilayer, multicolor element as described in example 2. This photographic element exhibits the improved physical properties discussed herein previously, including improved abrasion resistance.

My coatings in examples 1 through 22 exhibit substantially better abrasion resistance than the corresponding control coatings. Similarly, it can be shown that when other dye-forming couplers used in photography are dispersed in admixture with my polymeric dispersing agents illustrated herein that improved abrasion resistance is shown over corresponding control coatings.

ln photographic elements of my invention in which there is a need for incorporating a hydrophobic ultraviolet absorbing compound in one or more of the layers, it is advantageous to use dispersions of mixtures of the desired hydrophobic ultraviolet absorber and a polyvinyl resin. Resins useful for this include poly alkyl acrylates, poly alkyl methacrylates, poly vinyl acetals, poly(alkyl acrylate alkyl methacrylate), poly(vinyl-acetal vinyl alcohol vinyl acetate), etc. Especially efficacious water-insoluble ultraviolet absorbing compounds include substituted 4-thiazolidones (e.g., S-benzylidene-J-hexadecyl-2-phenylimino-4-thiazolidone, 5-benzylidene-3-phenyl-2-phenylimino-4-thiazolidone, 2-( 2,6-diethylphenylimino)- 3-hexadecyl-5-( 2-methoxybenzylidene )-4-thiazolidone, 2- (2,6-diethylphenylimino )-3-hexadecyl-5-( 2-methylbenzylidene)-4-thiazolidone, 3-( 2,6-diethylphenyl )-2-( 2,6- diethylphenylimino )-5-( 4-dodecylbenzylidene )-4- thiazolidone, 2-( 2,6-diethylphenylimlno)-5-( 2,5-dimethylbenzylidene )-3-( 3,5-dimethylphenyl )-4-thiazolidone, etc. certain substituted benzotriazoles (e.g.. 2-( 2-hydroxy-3,5-di-tamylphenyl)benzotriazole, 2-(2 -hydroxy-S-iso-octylphenyl)- S-methylbenzotriazole, etc. substituted thiazolol5,4-d] thiazoles (e.g., 2,5-bis(2-decyloxyphenyl)thiazolol5,4- dlthiazole, Z-(p-dodecylphenyl)-4.5-acenaphthenotraizole,

etc. etc. The mixture of ultraviolet absorbing compound and polymeric dispersing agent is advantageously dispersed in hydrophilic colloid binders conventionally used in photographic elements. These ultraviolet absorbing dispersions are especially efficacious when the hydrophilic colloid binder is gelatin hardened with aziridine derivatives of poly phosphonitriles and when a ureido coumarin optical brightener such as those described in British Pat. No. 786,234 is incorporated to further reduce stain and further improve whiteness.

Use of my hydrophobic coupler-polymer dispersions in photographic emulsion layers provides valuable technical advance, as has been described in the above specification. These dispersions are especially advantageous for coating in thin layers because of their greatly increased structural rigidity and resistance to abrasion. My polymeric dispersing agents protect the couplers and dyes (formed from the couplers) from exposure to light and detrimental affects from exposure to chemicals in the photographic element and solutions used in the photographic processing of these elements. It is surprising that the polymeric dispersing agents would protect the couplers and dyes from the affect of ultraviolet light exposure since the polymers are transparent to ultraviolet light. In addition to the valuable characteristics that my polymeric dispersing agents impart to coupler dispersions mentioned above, my dispersing agents are admirably suited for incorporating couplers in photographic emulsion layers.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

lclaim:

l. A photographic element comprising a paper support having coated in succession on one side,

A. a blue-sensitive emulsion comprising gelatin having substantially uniformly, separately dispersed therein (1) blue-sensitive silver chlorobromide grains and (2) finely divided particles having an average diameter of less than 5 microns of a mixture of one part by weight of a-pivalyl- 2-chloro-5-[ 2,4-di-t-amylphenoxy)butyramidola cetanilide and two parts by weight of poly(butyl methacrylate 85 percent acrylic acid percent),

B. a green-sensitized emulsion comprising gelatin having substantially uniformly. separately dispersed therein (1) green-sensitized silver chlorobromide grains and (2) finely divided particles having an average diameter of less than 5 microns of a mixture comprising one part by weight of l-( 2-chloro-4,6-dimethylphenyl)-3-{ 3-[0l-(pentadecylphenoxy)-butyramido]benzamido l-S-pyrazolone and one quarter part by weight of poly(butyl acrylate 85 percent acrylic acid 15 percent). and

C. a red-sensitized emulsion comprising gelatin having sub stantially uniformly, separately dispersed therein l redsensitized silver chlorobromide grains and (2) finely divided particles having an average diameter of less than 5 microns of a mixture comprising four parts by weight of 2-[a-( 2,4-di-t-amylphenoxy)butyramido]-4,6-dichloro-5- methylphenol and one part by weight of poly(butyl acrylate 85 percent acrylic acid 15 percent).

2. A photographic color-forming light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly, separately dispersed therein (I) lightsensitive silver halide grains, and (ll) particles having anaverage diameter of less than 5 microns comprising A. a hydrophobic color-forming photographic coupler; and

B. a water-insoluble, organic solvent-soluble polymer containing recurring units having the formula:

wherein R represents a member selected from the class consisting of hydrogen and -CH,; and R, represents an alkyl group having from one to 22 carbon atoms; together with recurring units of at least one ofthe formulas:

(2) CII2$ R O=C-OH and (3) CH,C R-

l R: O=Ct) C Z;

wherein R and R each represent a member selected from the class consisting of hydrogen, an alkyl group and an alkoxy group; n represents an integer of from I to 22; Z represents a group selected from the class consisting of a -OSO,X group, a -SO;,X group and a -CO X group in which X is selected from the class consisting of hydrogen, sodium, potassium and NH R is as defined previously;

4) -CH1CH O=:( Nll; (5) -CH2C]I- O=( ]-ORi wherein R is defined previously; (6) CH;

CII1(IJ 0=o-NnN1icciI2cN CIIz( J- 0 O=( JOClI CII O( TiCH; CH; (8) -CII.'9II

wherein R is as defined previously; (9) Cl1,C1I-

and (10) -CII;(|I1I 11 0 \C=O HQC JH1 wherein R represents a member selected from the class consisting of hydrogen and alkyl having from one to eight carbon atoms.

3. A photographic color-fonning light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly, separately dispersed therein (I) lightsensitive silver halide grains, and (ll) finely divided particles of a substantially water-immiscible mixture comprising (A) a hydrophobic color-forming photographic coupler and (B) a water-insoluble, organic solvent-soluble polymer containing recurring units having the formula:

wherein R, represents an alkyl group having from one to 22 carbon atoms; together with recurring units of at least one of the formulas:

wherein R, and R each represent a member selected from the class consisting of hydrogen, an alkyl group and an alkoxy group; n represents an integer of from I to 22; Z represents a group selected from the class consisting of a -OSO,X group, a SO;X group and a CO,X group in which X is selected from the clas consisting of hydrogen, sodium, potassium and NH (1) CH:C H-

O(IJORI wherein R represents an alkyl group having from one to 22 carbon atoms, and about 60 to about 2 mole percent of recurring units selected from the class consisting of those having the formulas:

wherein R, and R, each represent a member selected from the class consisting of hydrogen, an alkyl group. and an alkoxy group; n represents an integer of from I to 22; and Z represents a group selected from the class consisting of a -OSO,X group. a -SO,X group and a CO X group in which X is selected from the class consisting of hydrogen, sodium, potassium and NH said particles having an average diameter of less than 5 microns.

5. A photographic color-forming light-sensitive emulsion of claim 4 in which the hydrophilic colloid binder is gelatin.

6. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (l a hydrophobic color-forming coupler selected from the class consisting of a S-pyrazolone coupler, a phenolic coupler. a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble organic-solvent soluble poly(butyl acrylate acrylic acid), said particles having an average diameter ofless than 5 microns.

7. A photographic color-forming light-sensitive emulsion of claim 6 in which the poly(butyl acrylate acrylic acid) contains about mole percent butyl acrylate.

8. A photographic color-forming light-sensitive emulsion comprising av film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising l a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler. a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(butyl acrylate 3-acryloxy-butane-lsulfonic acid sodium salt), said particles having an average diameter of less than 5 microns.

9. A photographic color forming light-sensitive emulsion of claim 8 in which the poly(butyl acrylate 3-acryloxybutane'lsulfonic acid sodium salt) contains about 85 mole percent butyl acrylate.

10. A photographic colorforming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (l) a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler, a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(butyl acrylate stearyl methacrylate acrylic acid), said particles having an average diameter of less than 5 microns.

ll. A photographic color-forming light-sensitive emulsion of claim 10 in which the poly(butyl acrylate stearyl methacrylate acrylic acid) contains about 60 mole percent butyl acrylate, and about 25 mole percent stearyl methacrylate.

12. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (l a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler. a phenolic coupler, a

naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble. organic-solvent soluble poly(methyl acrylate acrylic acid). said particles having an average diameter of less than 5 microns.

IS. A photographic color-forming light-sensitive emulsion of claim 12 in which the poly(methyl acrylate acrylic acid) contains about percent methyl acrylate.

14. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (l a hydrophobic color-forming coupler selected from the class consisting of a S-pyrazolone coupler. a phenolic coupler. a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(butyl acrylate cetyl vinyl ether acrylic acid), said particles "having an average diameter of less than 5 microns.

[5. A photographic color-forming light-sensitive emulsion of claim 14 in which the poly(butyl acrylate cetyl vinyl ether acrylic acid) contains about 64 mole percent butyl acrylate' and about 15 mole percent acrylic acid.

l6. A photographic element comprising a support coated with at least one color forming light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly dispersed therein (l) light-sensitive silver halide grains, and (ll) particles having an average diameter of less than 5 microns comprising A. a hydrophobic color-forming photographic coupler and B. a water-insoluble, organic solvent-soluble polymer containing recurring units having the formula:

wherein R represents a member selected from the class consisting of hydrogen and CH R, represents an alkyl group having from one to 22 carbon atoms; together with recurring units of at least one of the formulas:

wherein R and R each represent a member selected from the class consisting of hydrogen, an alkyl group and an alkoxy group; n represents an integer of from 1 to 22; Z represents a group selected from the class consisting of a -OSO -,X group, a -SO;,X group and a -CO X group in which X is selected from the class consisting of hydrogen. sodium, potassium and NH R is as defined previously;

i i i mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3,619,195 Dated November 9, 1971 Inventor) John VanCampen It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 20, Claim 2, line 6, replace the formula with -CH -CH- I R 2 (3) O=C-O-C -Z Column 23, Claim 16, line 13, replace the formula with 2 (1) O=COR Claim 16, line 20, replace the formula with -CH2-CR- Column 2, Claim 17, line 31, delete "(2,U-di-t-amylphenoxy)" and insert -(2,U-di-1; -amylphenoxy); Claim 18, line 30, after "dimethyl-phenyl)-3" insert line 35, after "benzamido" insert Claim 19, line 37, change "-t" to t Signed and sealed this 6th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. A photographic color-forming light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly, separately dispersed therein (I) light-sensitive silver halide grains, and (II) particles having an average diameter of less than 5 microns comprising A. a hydrophobic color-forming photographic coupler; and B. a water-insoluble, organic solvent-soluble polymer containing recurring units having the formula: wherein R represents a member selected from the class consisting of hydrogen and -CH3; and R1 represents an alkyl group having from one to 22 carbon atoms; together with recurring units of at least one of the formulas:
 3. A photographic color-forming light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly, separately dispersed therein (I) light-sensitive silver halide grains, and (II) finely divided particles of a substantially water-immiscible mixture comprising (A) a hydrophobic color-forming photographic coupler and (B) a water-insoluble, organic solvent-soluble polymer containing recurring wherein R1 represents an alkyl group having from one to 22 carbon atoms; together with recurring units of at least one of the formulas:
 4. A photographic color-forming light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly, separately dispersed therein (I) light-sensitive silver halide grains, and (II) finely divided particles of a substantially water-immiscible mixture comprising (A) a hydrophobic color-forming photographic coupler and (B) a water-insoluble, organic solvent-soluble polymer containing from about 40 to about 98 mole percent of recurring units having the formula: wherein R1 represents an alkyl group having from one to 22 carbon atoms, and about 60 to about 2 mole percent of recurring units selected from the class consisting of those having the formulas:
 5. A photographic color-forming light-sensitive emulsion of claim 4 in which the hydrophilic colloid binder is gelatin.
 6. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (1) a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler, a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble organic-solvent soluble poly(butyl acrylate acrylic acid), said particles having an average diameter of less than 5 microns.
 7. A photographic color-forming light-sensitive emulsion of claim 6 in which the poly(butyl acrylate acrylic acid) contains about 85 mole percent butyl acrylate.
 8. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (1) a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler, a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(butyl acrylate 3-acryloxy-butane-1-sulfonic acid sodium salt), said particles having an average diameter of less than 5 microns.
 9. A photographic color-forming light-sensitive emulsion of claim 8 in which the poly(butyl acrylate 3-acryloxybutane-1-sulfonic acid sodium salt) contains about 85 mole percent butyl acrylate.
 10. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (1) a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler, a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(butyl acrylate stearyl methacrylate acrylic acid), said particles having an average diameter of less than 5 microns.
 11. A photographic color-forming light-sensitive emulsion of claim 10 in which the poly(butyl acrylate stearyl methacrylate acrylic acid) contains about 60 mole percent butyl acrylate, and about 25 mole percent stearyl methacrylate.
 12. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (1) a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler, a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(methyl acrylate acrylic acid), said particles having an average diameter of less than 5 microns.
 13. A photographic color-forming light-sensitive emulsion of claim 12 in which the poly(methyl acrylate acrylic acid) contains about 90 percent methyl acrylate.
 14. A photographic color-forming light-sensitive emulsion comprising a film-forming gelatin binder having substantially uniformly, separately dispersed therein (A) light-sensitive silver halide grains and (B) finely divided particles of a substantially water-immiscible mixture comprising (1) a hydrophobic color-forming coupler selected from the class consisting of a 5-pyrazolone coupler, a phenolic coupler, a naphtholic coupler and an open-chain coupler having an active methylene group and (2) a water-insoluble, organic-solvent soluble poly(butyl acrylate cetyl vinyl ether acrylic acid), said particles having an average diameter of less than 5 microns.
 15. A photographic color-forming light-sensitive emulsion of claim 14 in which the poly(butyl acrylate cetyl vinyl ether acrylic acid) contains about 64 mole percent butyl acrylate and about 15 mole percent acrylic acid.
 16. A photographic element comprising a support coated with at least one color-forming light-sensitive emulsion comprising a film-forming hydrophilic colloid binder having substantially uniformly dispersed therein (I) light-sensitive silver halide grains, and (II) particles having an average diameter of less than 5 microns comprising A. a hydrophobic color-forming photographic coupler and B. a water-insoluble, organic solvent-soluble polymer containing recurring units having the formula: wherein R represents a member selected from the class consisting of hydrogen and -CH3; R1 represents an alkyl group having from one to 22 carbon atoms; together with recurring units of at least one of the formulas:
 17. A photographic element of claim 16 in which the said hydrophobic color-forming coupler is Alpha -pivalyl-2-chloro-5-( gamma -(2,4-di-t-amylphenoxy)butyramido)acetanilide.
 18. A photographic element of claim 16 in which the said hydrophobic color-forming coupler is 1-(2-chloro-4,6-dimethyl-phenyl)-3- 3-( Alpha -pentadecylphenoxy)butyramido)benzamido -5-pyrazolone.
 19. A photographic element of claim 16 in which the said hydrophobic color-forming coupler is 2-( Alpha -(2,4-di-t-amylphenoxy)butyramido)-4,6-dichloro-5-methylphenol. 